Process of creaseproofing cellulosic textiles with a single aqueous solution containing both d, l-butadiene dioxide and a lewis base catalyst



United States Patent PROCESS OF CREASEPROOFKNG CELLULOSIC TEXTILES WITH A SINGLE AQUEOUS SOLU- TION CONTAINING BOTH d,l-BUTADlENE DIGXIDE AND A LEWIS BASE CATALYST Ralph J. Berni, Ruth R. Benerito, and John B. McKelvey, New Orleans, La, assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed Aug. 27, 1965, Ser. No. 483,372 1 Claim. (Ci. 8-120) and various Lewis bases in aqueous media. Utility of the present invention is found in the fact that the cellulosic fabrics produced by process of this invention show improved dry and wet crease recovery without unduly altering the strength, hand, or appearance of the finished fabric.

The primary object of the invention is to produce butadiene diepoxide etherified cotton fabrics exhibiting improved crease recovery properties by means of an all aqueous treatment. Prior art processes utilized 2- or 3- phase systems to produce crease resistant fabrics. Practical processes utilizing all-aqueous systems are preferred in commercial proceses over nonaqueous systems.

Another object of this invention is to provide a process for etherifying cotton fabrics with butadiene dioxides, which can produce fabrics with moderate increases of dry crease recovery, for example, those in the 240 to 250 (W plus F) range; and moderate to large increases in wet recovery, for example, those in the 240 to 280 (W plus F) range. Prior art processes have produced ex cessive increases in crease recovery, which have proved to be unfavorable in subsequent garment cutting operations.

A third object of this invention is to provide an etherification process which utilizes general base catalysis, since combined processes (dyeing, softening, calendering,

etc.) involve restrictions in use of strong caustic solutions, therefore weaker bases are indicated.

In general, according to our present invention a cellulosic material, such as cottom (0.06 mole), is reacted by immersing for a period of time about from minutes to 24 hours in a solution containing about from 0.125 to 0.250 mole of butadiene dioxide and sufiicient water to make 100 ml., and catalyzed with about from 0.01 to 0.03 mole of a Lewis base selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, aniline, pyridine, piperidine, morpholine, quinoline, cyclohexylamine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 3 pyridol, monoethanolarnine, diethanolarnine, and triethanolamine,

and a cottom fabric which possesses improved wet and dry crease resistance is obtained. The applicable molar ratios are about from 1:2:.l6 to 124:.50, anhydrogluoose units of cellulose to butadiene dioxide to catalyst, respectively.

Prior art processes required more expensive nonaqueous systems for producing dry and wet crease recovery on cotton using d,1-butadiene dioxide in basic or acidic media. Our present invention takes advantage of the surface polymerization as well as the crosslinking mechanisms to obtain products which produce improved dry and wet recovery for cotton cellulose at. room temperature.

The term Lewis base is defined as any molecule or ion having unshared electron pairs available for sharing with acids. All of the bases mentioned in this application are included in this classification, and all catalyze the etherification (cellulose butadiene dioxide reaction) with varying degrees of efiiciency.

The preferred method for obtaining the desired results consists in complete immersion of an x 80 or a 68 x 72 cotton fabric into a container filled with m1. of an aqueous solution containing from 0.125 to 0.250 mole of d,l-butadiene dioxide, and from 0.01 to 0.03 mole of a catalyst or coreactant Lewis base, and reacted at ordinary room temperature (20 to 30 C.) for a period of from about 10 minutes to 24 hours. The sequence of solution preparation is critical in that the water and butadiene dioxide must be first combined before addition of the catalyst since the addition of catalyst to the con centrated epoxide would cause rapid polymerization thereby destroying the reaction media. After the etherified cotton is removed from the reaction vessel the fabric is quenched in a weakly acidic solution, washed in tap water, and distilled water, and ironed dry. The fabric obtained exhibits increased dry (conditioned) and wet recovery without surrendering its basic fabric properties.

Dry crease recovery evaluations are expressed in degrees, are a summation of Warp and Filling, and were done according to U.S. Federal Supply Service, Federal Specification CCC-T191b, Method 5212, Washington, D.C., U.S. Government Printing Oiiice (1951), while the wet crease recovery evaluations were determined by a method described by R. A. Fujirnoto, R. M. Reinhardt, and J. D. Reid in the American Dyestuff Reported, 52, P329 (1963). J

The examples set forth are meant to illustrate the practice of our present invention, and are not meant to be construed as limiting the invention in any manner whatever.

Example 1 A 10.0 gm. sample of 68 x 72 cotton fabric (0.06 mole) was rolled and placed in a. 100 ml. graduated cylinder containing 20 ml. of d,l-butadiene diepoxide (0.25 mole) and 1 30 gm. of NaOH (0.03 mole) diluted with distilled water'to 100 ml. The fabric was allowed. to remain immersedand react for 24 hours. The fabric sample was then removed from the solution, rinsed in methanol, neutralized with aqueous acetic acid, and quenched in tap water for at least 15 minutes, then ironed dry. The treated fabric sample had a weight add-on of 8.3%; and the dry and wet crease angles were respectively254" and 289 (W plus F).

Example 2 reaction times were employed. The significant data. are shown in Table I.

and molecular quantities used in the reaction, and results of significance to this invention.

TABLE II RESULTS Fabric Quantity Sample Reagent (moles) Add-On Crease Recovery (N 0.) (Percent) ry Wet 0. 02 4. 207 169 0. 01 5. 6 227 249 0. 02 6. 8 237 256 0. O1 6. 0 230 249 0. 02 8. 0 226 278 0. 01 2. 6 211 217 0. 02 3. 7 218 234 0. 01 3. 7 228 235 0 0.02 5.9 229 238 Benzyldimethylamlne 0. 01 5. 227 246 14 0 0. 02 7. 6 248 274 O. 01 3. 9 241 228 0. 01 6. 2 256 253 0. 01 6. 0 246 237 0. 01 3. 4 244 218 0. 01 8. 9 243 270 0. 02 9. 8 227 259 0. 01 7. 2 218 248 0. 02 9. 2 221 267 0. 02 5. 7 230 236 0. 01 4. 7 225 231 0. 01 3. 7 209 230 TABLE I Results Reaction Fabric Sample Time Crease Recovery Angles No. (minutes) Add-On (degrees, W plus 1*) (percent) Dry Wet 1 Crease recovery values are a summation of Warp and Filling angles, and are expressed in degrees.

2 Untreated sample.

Example 3 A 10.0 gm. (0.06 mole) sample of 68 x 72 cotton fabric was treated by the process of Example 1 except that aqueous ammonium hydroxide (0.030 mole) was used instead of aqueous sodium hydroxide to obtain a fabric with 7.6% add-on, and the dry and Wet crease angles were respectively 260 and 241 (W plus F).

Examples 4 through 25 Twenty-four 10.0 gm. (0.06 mole) samples of 68 x 72 cotton fabric were treated by the process of Example 1 except that an aqueous amine was used instead of aqueous sodium hydroxide. Table II shows the various amine References Cited UNITED STATES PATENTS 3,150,920 9/1964 Berni et al. 8-120 3,268,293 8/1966 McElVey et al. 812O OTHER REFERENCES Journal of Polymer Science, vol. 51, pp. 209-230 (1961) 8/120.

Journal of Polymer Science, part A, vol. 1, pp. 3407- 3426 (1963) 8/120.

Textile Research Journal, February 1963, pp. 117-129 8/ 120.

Journal of Polymer Science, vol. 9, pp. 181-190 (1965) 8/120.

Journal of Polymer Science, vol. 9, pp. 191205 (1965) 8/ 120.

NORMAN G. TORCHIN, Primary Examiner.

H. WOLMAN, Assistant Examiner. 

1. A PROCESS FOR IMPARTING IMPROVED WET AND DRY CREASE RECOVERY TO CELLULOSIC TEXTILE COMPRISING REACTING CELLULOSIC TEXTILE CONTAINING FREE CELLULOSIC HYDROXYL GROUPS BY IMMERSING SAID TEXTILE IN AN AQUEOUS SOLUTION CONSISTING ESSENTIALLY OF D,1-BUTADIENE DIOXIDE AND A LEWIS BASE CATALYST IN MOLAR RATIO OF FROM ABOUT 1:2:0.16 TO 1:4:0.50, RESPECTIVELY OF ANHYDROGLUCOSE UNITS OF CELLULOSE:D,1-BUTADIENE DIOXIDE:CATALYST, FOR A PERIOD OF TIME FROM ABOUT 10 MINUTES TO 24 HOURS AT ROOM TEMPERATURES, SAID AQUEOUS SOLUTION BEING PRODUCED BY DISSOLVING THE D,1-BUTADIENE DIOXIDE IN WATER AND THEN ADDING SAID CATALYST. 